Water → HCID 86653778, compound

HRID 1021205Notes

Reaction equation

HRID 1021205 reaction equation
[CH2:1]([O:8][C:9]1[C:16]([CH3:17])=[C:15]([CH3:18])[C:14]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[C:13]([CH3:27])[C:10]=1[CH:11]=[O:12])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[NH4+].[Cl-].CCOC(C)=O.O.[CH2:37]1[CH2:41]OC[CH2:38]1>>[CH2:1]([O:8][C:9]1[C:16]([CH3:17])=[C:15]([CH3:18])[C:14]([O:19][CH2:20][C:21]2[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=2)=[C:13]([CH3:27])[C:10]=1[CH:11]([OH:12])[CH2:41][CH:37]=[CH2:38])[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 5

HCID 962WaterHCID 8028Tetrahydrofuran3×HCID 8857Ethyl Acetate2×HCID 25517Ammonium ChlorideHCID 86653777HCID 86653777, compound

Product 1

HCID 86653778HCID 86653778, compound

Conditions

Temperature
0 °C

Procedure

2,5-Bis(benzyloxy)-3,4,6-trimethylbenzaldehyde (3.90 g, 12.16 mmol) was dissolved into 50 mL THF and cooled to 0° C. prior to the addition of 15 mL allyl Grignard (1.0 M in THF, 15 mmol). The pale yellow solution browned over the course of the addition. After 15 minutes at 0° C. the reaction was not complete by HPLC and an additional portion of allyl Grignard (3 mL, 1.0 M in THF, 3 mmol) was added and stirred for 0.6 h at which time the reaction was judged complete by HPLC. The reaction was treated carefully at 0° C. with 50 mL 10% aqueous NH4Cl stirred for five minutes post addition and 100 mL EtOAc added. The layers were stirred vigorously until they clarified, an additional 100 mL H2O and 100 ml EtOAc was added, the layers separated and the aqueous phase extracted 3×100 mL EtOAc. The combined organics were washed with 2×50 mL saturated aqueous NaCl and dried over Na2SO4 prior to concentration to a pale brown oil. Storage under vacuum gave a brown solid. Flash chromatography (gradient elution 0-20% EtOAc/heptane) yielded 3.91 g of 1-(2,5-bis(benzyloxy)-3,4,6-trimethylphenyl)but-3-en-1-ol as a white, waxy solid. M++H—H2O=385 m/z; 1H NMR (400 MHz, CDCl3) δ=7.55 (d, 4 H), 7.51-7.42 (m, 6 H), 5.91 (m, 1H), 5.19-5.10 (m, 3 H), 5.01 (d, 1 H), 4.90 (d, 1 H), 4.78 (s, 2 H), 3.35 (d, 1 H), 2.76 (m, 1 H), 2.55 (m, 1 H), 2.39 (s, 3 H), 2.32 (s, 3 H), 2.31 (s, 3 H) ppm.

Workup

  1. additionThe pale yellow solution browned over the course of the addition
  2. additionadded
  3. stirringThe layers were stirred vigorously until they
  4. customthe layers separated
  5. extractionthe aqueous phase extracted 3×100 mL EtOAc
  6. washThe combined organics were washed with 2×50 mL saturated aqueous NaCl
  7. dry with materialdried over Na2SO4
  8. concentrationto concentration to a pale brown oil
  9. customStorage under vacuum gave a brown solid
  10. washFlash chromatography (gradient elution 0-20% EtOAc/heptane)

Sources & evidence

ORD record
ord-e56378a56ebd4555a19b31a01f3b113e
Source dataset
uspto-grants-2014_05
Patent number
US08716527B2

Reaction notes

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